Organoaluminum compounds and their preparation

ABSTRACT

Organoaluminum compounds possessing a vinylic aluminaazacyclopentene moiety are described. They are prepared by reacting a nonionic organoaluminum compound possessing an aluminacyclopenetene moiety with a nitrile in the presence of a stable Lewis base. The compound possessing the vinylic aluminaazacyclopentene moiety yield on hydrolysis olefinically unsaturated ketimines or ketones depending upon the conditions used in effecting the hydrolysis. Oxidation of the moiety followed by hydrolysis yields olefinically unsaturated ketones having a hydroxyl group in the beta position relative to the keto group.

United States Patent [191 Shepherd, Jr.

[451 Jan. 21, 1975 1 1 ORGANOALUMINUM COMPOUNDS AND THEIR PREPARATION[75] Inventor: Lawrence ll. Shepherd, Jr., Baton Rouge, La.

[73] Assignee: Ethyl Corporation, Richmond, Va.

[22] Filed: Nov. 2, 1973 [21] Appl. No.: 412,179

[52] U.S. Cl. 260/448 A, 260/270 K, 260/299, 260/326.8, 260/340.6,260/340.9, 260/345.1, 260/566 R, 260/590, 260/593 R [51] Int. Cl. C07f5/06 [58] Field of Search 260/448 R, 448 A, 340.6, 260/340.9, 270 R,299, 326.8, 345.1

[56] References Cited UNITED STATES PATENTS 3,631,065 12/1971 Brendel etal. 260/448 A 3,634,482 1/1972 3 Shepherd 260/448 A 3,641,084 2/1972Shepherdm. 260/448 A 3,755,400 8/1973 Shepherd 260/448 A OTHERPUBLICATIONS Ncsmcyanov et al., Methods of Elemento-Organic Chemistry,Vol. 1, pp. 468 & 469, 415 & 416.

Zeiss, Organometallic Chemistry, Reinhold Publ. Corp., N.Y.. PP-236-238. (1960).

Primary Examinerl-l. Sneed Attorney, Agent, or Firm-Donald L. Johnson;John F. Sieberth [57] ABSTRACT sis. Oxidation of the moiety followed byhydrolysis.

yields olefinically unsaturated ketones having a hydroxyl group in thebeta position relative to the keto group.

23 Claims, N0 Drawings ORGANOALUMINUM COMPOUNDS AND THEIR PREPARATIONThis invention relates to cyclic organoaluminum compounds and theirpreparation.

This invention involves. inter alia. the discovery that thealuminacycloalkene compounds of the type described in US. Pat. No.3.63l.()65 react with nitriles to produce another class of cyclicaluminum compounds. The reaction in question involves the 1:] molecularaddition as between the aluminacyclopent-3-ene moiety and the nitrilewhereby there is formed an organoaluminum compound possessing a4-vinylic-( l-alumina-2- azacyclopent-Z-ene) moiety having acarbon-bonded substituent in the 3 position. This cyclic moiety isattached by means of an aluminum-carbon bond to an organic group whichin the ordinary situations will have no more than about 18 carbon atoms.For best results the reaction is performed in the presence of a stableLewis base--i.e., a Lewis base not susceptible to excessive cleavageduring the course of the reaction. Since, as pointed out more fullyhereinafter, the reaction can be performed under very mild reactionconditions, a wide variety of Lewis bases including tertiary amines,ethers. and other similar substances may be used for this purposewithout encountering excess cleavage. Tertiary amines, dialkyl ethers,cycloparaffinic monoethers having a six-membered ring or cycloparaffinicdiethers having a fiveor six-membered ring exemplify preferred Lewisbases.

Accordingly, in one embodiment this invention pro vides a process ofpreparing an organoaluminum compound possessing a 4-vinylic-(l-alumina-2- azacyclopent-Z-ene) moiety which comprises reacting (i) anonionic organoaluminum compound possessing an aluminacyclopent-3-enemoiety, the moiety being attached by means of an aluminum-carbon bond toa hydrocarbon group which optionally may be substituted by no more thanone additional so-bonded aluminacyclopent-3-ene moiety, with (ii) anitrile co-s reactive therewith so that 1:] addition occurstherebetween, the reaction being conducted in the presence of a stableLewis base. From the cost effectiveness standpoint the preferred cyclicaluminum reactants are those in which each aluminacyclopent-3-ene moietyhas the formula wherein R is a hydrogen, alkyl or alkenyl group, R is ahydrogen or alkyl group, and al is two-thirds of an equivalent ofaluminum.

A feature ofthis invention is that the foregoing reaction is a facilereaction which can be readily carried out under mild reactionconditions. In fact, the reaction proceeds very smoothly and efficientlyeven at room temperature and thus all that is required is to bring thereactants together in the presence of the Lewis base in a suitablyinert. anhydrous reaction environment. Although the reaction can. ifdesired. be carried out at elevated temperatures as high as about l75C.(so long as competing reactions do not occur excessively) there is nosignificant advantage in doing so-reactions performed at temperatureswithin the range of from about 0" t o C. are generally found mostconvenient. Re-J actions at even lower temperatures as possible, thoughless convenient and generally slower.

A wide variety of nitriles can be employed in the foregoing process.including mononitriles and polynitriles. The only requirement is thatthe nitrile reactant be free from substituent groups which would preventor seriously interfere with the desired l:l addition reaction such ashydroxyl groups. primary amino groups. carboxy groups and the like. Thenitriles may be saturated or unsaturated and may contain substituentswhich are relatively inert to the aluminacyclopent- 3-ene moiety at thereaction temperatures being used (room temperature, for example) such ashalogen atoms in non-activated positions, tertiary amino groups (i.e.,amino groups not containing nitrogen-hydrogen bonds), ether linkages,thioether linkages, R Si groups, R P-- groups, RSegroups, XMgO- groups(X halogen), R SiO- groups, and the like. In short, use may be made ofany organic nitrile capable of reacting with the aluminacyclopent-S-enemoiety via a 1:1 addition reaction at a reaction temperature somewherebetween about 0 and 100C. to form a 4-vinylic-(l-alumina-Z-azacyclopent-Z-ene) moiety having a substituent in the 3position corresponding to that to which a cyano group was attached inthe nitrile reactant. Thus. functional substituents may be present inthe nitrile reactant as long as they are innocuous in the sense they donot prevent the formation of the 4- vinylic-(l-alumina-2-azacyclopent-2-ene) moiety nor interfere with the existenceof this moiety once it has been formed. For example, nitriles havingfunctional groups containing labile hydrogen atoms (e.g., hydroxyl,primary and secondary amino, hydrazino, isonitroso. sulfamino, mercapto.imino, etc.) or functional groups containing reactive double bondsbetween dissimilar atoms (e.g., carbonyl, nitro, nitroso, sulfinyl,sulfonyl, thiocarbonyl, etc.) are ordinarily not recommended for use inthe process. The suitability of any given nitrile for use in the processcan readily be determined by the simple expedient of performing a fewpilot experiments using, for instance, the procedure set forth in theExample given hereinafter.

A few exemplary nitriles for use in the process include acetonitrile,propionitrile, butyronitrile, isobutyronitrile, valeronitrile,alphamethylbutyronitrile. isocapronitrile, alphaethylbutyronitrile,caprylonitrile, succinonitrile, glutaronitrile, acrylonitrile,methacrylonitrile, allyl cyanide, 4-

pentenenitrile benzylcyanide, benzonitrile, otolunitrile, m-tolunitrile,p-tolunitrile, 2- bromobenzonitrile, 3-bromobenzonitrile, 4-

bromobenzonitrile, isophthalonitrile, ladamantanecarbonitrile.cinnamonitrile, 3,7-dimethyl- 2,6-octadienenitrile, alpha-ethyll-cycloheptenel acetonitrile, nonadecanenitrile, anisonitrile, 9-anthracenecarbonitrile, anthranilonitrile, lnaphthylacetonitrile,Z-naphthylacetonitrile. 5-

dimethylaminoanthranilonitrile,benzylidenemalononimethoxyphenyl)-acetonitrile,l-(p-methoxyphenyl)-lcyclohexanecarbonitrile, l-( p-methoxyphenyU- lo-tolunitrile, 2-norbornanecarbonitrile, tetracyanoethylene,tetrachlorophthalonitrile, 4- bromobutyronitrile, 4-bromo-2,2-

diphenylbutyronitrile, p-bromophenylacetonitrile, 3- bromopropionitrile,alpha-bromo-o-tolunitrile, alphabromo-n-tolunitrile,alpha-bromo-p-tolunitrile, 5 bromovaleronitrile,m-flurophenylacetonitrile, pfluorophenylacetonitrile, fumaronitrile, 2-

furanacetonitrile, Z-furanacrylonitrile, 2-furonitrile,tetradecanedinitrile, tetrafluoroterephthalonitrile, 2,3,-5,6-tetramethyl-p-benzenediacetonitrile, phenyl-2- pyridylacetonitrile,3-pyridylacetonitrile, n-heptyl cyanide, 2-chloro-6-methylbenzonitrile,3-chloro-4- methylbenzonitrile, p-chloro-alphamethylphenylacetonitrile,3-chloro-2- l-cyanonaphthalene, 9- cyanophenanthrene,2,3,4-trimethoxybenzonitrile, 2,4,6-trimethoxybenzonitrile,3,4,5-trimethoxybenzonitrile, 3,4,5-trimethyoxyphenylacetonitrile,iodoacetonitrile, alphamethylbenzyl cyanide, 2- methylbenzyl cyanide,3-methylbenzyl cyanide, 4- methylbenzyl cyanide, l-(p-chlorophenylJ-lcyclobutanecarbonitrile, l-(p-chlorophenyU-lcyclohexanecarbonitrile,l-(p-chlorophenyl)-lcyclopentanecarbonitrile,l-(p-chlorophenyl)-lcyclopropanecarbonitrile, 3-chloropropionitrile, 5-chlorovaleronitrile, 5-norbornene-Z-carbonitrile, noctyl cyanide,betaphenylcinnamonitrile, l-phenylcyclobutanecarbonitrile,l-phenyl-lcyclopropanecarbonitrile, trichloroacetonitrile,dibromoacetonitrile, 2,6-dichlorobenzonitrile, 3,5-dichlorobenzonitrile, 2-cyanoethyl ether,l-(p-tolyl)-lcyclohexanecarbonitrile,l-(p-tolyl)-lcyclopentanecarbonitrile,]-(p-tolyl)-lcyclopropanecarbonitrile, dodecanedinitrile,(l-ethoxyethylidene)malononitrile, ethoxymethylenemalononitrile,3-cyclohexene-l-carbonitrile, lcyclohexenylacetonitrile,tridecanenitrile, diphenylacetonitrile, 2,2-diphenylpropionitrile,trans-1- cyano-2-phenylcyclopropane, cyclohexylphenylacetonitrile,l-cyclopenteneacetonitrile, cyclopropyl cyanide,2-thiopheneacetonitrile, 2-thiopheneacrylonitrile,2-thiophenecarbonitrile, 2,3-dimethoxybenzonitrile,2,4-dimethoxybenzonitrile, 3,4-dimethoxybenzonitrile,3,5-dimethoxybenzonitrile, 3,4dimethoxycinnamonitrile,(3,4-dimethoxyphenyl)- acetonitrile, Z-Cyanopyridine, 3-cyanopyridine,and 4- cyanopyridine. Hydrocarbyl mononitriles (e.g., nitrilescontaining up to about 24 carbon atoms in the molecule) serve as onetypical group of preferred nitrile reactants for use in the process ofthis invention.

As noted above the cyclic organoaluminum compounds provided by thisinvention possess a 4-vinylic- (l-alumina-2-azacyclopent-2-ene) moiety,the moiety being attached by means of an aluminum-carbon bondmethylpropionitrile,

to an organic group which normally will contain up to about 18 carbonatoms. In addition to the vinylic substituent in the 4 position, themoiety will contain a substituent in the 3 position corresponding to theorganic group to which the cyano group was attached in the nitrilereactant. For example when the nitrile reactant is acetonitrilecyanocyclopropane, glutaronitrile, benzyl cyanide, andp-bromobenzonitrile the substituent in the 3 position of the resultant4- vinylic( l-alumina-2- azacyclopent-Z-ene) moiety formed in therespective 1:] addition reactions is methyl, cyclopropyl, 3-cyanopropyl, benzyl and p-bromphenyl, respectively. Thus, this inventionprovides an organoaluminum compound possessing a 4-vinylic( l-alumina-Z-azacyclopent-Z-ene) moiety having an innocuous carbon bonded substituentin the 3 position, innocuous in the sense that it did not prevent theformation of the moiety nor interfere with the existence of the moietyonce it was formed. A few exemplary moieties of this type include thosein which the substituent in the 3 position is a hydrocarbyl substituenthaving up to about 18 carbon atoms, the vinylic substituent in the 4position being the vinyl group, the isopropenyl group, the lethylvinylgroup, or the 1-(4-methyl-pent-3-enyl )vinyl group. The 4 position inthe moiety can contain another substituent in addition to the vinylicsubstituent. One group of such compounds is those in which the 3position carries a hydrocarbyl substituent having up to about 18 carbonatoms and the 4 position contains an isopropenyl group and amethylgroup.

The organic group bonded by means of an aluminumcarbon bond to thealuminum atom in the 4-vinylic-( lalumina-Z-azacyclopent-Z-ene) moietywill generally correspond to the hydrocarbon group present in theinitial aluminacyclopent-3-ene reactant and accordingly for furtherdetails reference may be had to US. Pat. Nos. 3,631,065; 3,634,482; and3,755,400, each of which deals, inter alia, with the synthesis oforganic compounds containing the aluminacyclopent-3-ene moiety. All suchcompounds are suitable for use in the practice of this invention and inthe usual case the identity of the organic group satisfying theremaining valence bond of the aluminum atom in thealuminacyclopent-3-ene moiety is of no practical significance. Normallythis organic group which satisfies the third va lence bond of thealuminum atom may be regarded as excess baggage" which does not affectthe outcome of the desired addition reaction.

One preferred group of cyclic aluminum reactants for use in the processof this invention has the formula A 5 2C CH2 wherein R is a hydrocarbongroup having up to about R1 R2 thesis of various poly-functionalproducts. For exam- I v ple, on hydrolysis the compounds ofthisinvention yield CH =CC C- -R olefinically unsaturated ketimines orketones dependl 4 3 ll ing upon the conditions used in effecting thehydrolysis. 2 5 2 N 5 Thus, if mild hydrolysis conditions are used(e.g., hy-

1 drolysis with water or dilute acid at 0 to 5C.) the i product isgenerally a ketimine. On the other hand, R when the hydrolysis iscarried out under more stringent reaction conditions (e.g., hydrolysisat temperatures in wherein R is a hydrocarbon group having up to aboutthe range of 50 to 100C.) an olefinically unsaturated 18 carbon atoms(most preferably a lower alkyl group), ketone is formed. Alternatively,the cyclic organoaluand in the simplest cases R is hydrogen or an alkylor minum compounds of this invention may be subjected alkenyl group, Ris hydrogen or an alkyl group, and R to low temperature oxidation withair or oxygen to is an innocuous carbon-bonded organic group havingyield a cyclic alkoxide intermediate which, on hydrolyup to about 30carbon atoms, such as a hydrocarbyl 5 sis, yield. olefinicallyunsaturated ketones having a hygroup having up to about 30 carbon atoms.Preferably, droxyl group in the beta position relative to the keto R,,has up to about 18 carbon atoms. Since it is convegroup. The oxidationof the substituted l-alumina-2- nient to utilize diisobutylaluminumhydride or sodium azacyclopent-2ene moiety to form the correspondingaluminum tetraethyl in the synthesis of the cyclic alkoxide moiety(l-alumina-2-aza-6- aluminocylopent-B-ene moiety containing compounds 20oxacyclohex-2-ene) utilizes reaction conditions such as used to form theorganoaluminum compounds depicted des ri d i .8 5. in the above formula(see U.S. Pat. Nos. 3,631,065 and In order to further appreciate thepractice and advan- 3,634,482, respectively) R in the above formula willtages ofthis invention there are presented below in tabfrequently beisobutyl or ethyl. ular form somev typical products which may be pro-There is a marked tendency for the cyclic aluminum dUCe y Some Of thereactions bed abovecompounds of this invention to form complexes withThe transformations set forth in the tabulation give Lewis bases such asamines, ethers, thioethers, and the some indication of the varietyofproducts which can like. These complexes, especially when the Lewisbase now be readily produced by virtue of this invention. It is atertiary amine, dialkyl ether, cycloparaffinic monowill be appreciatedof course that it is possible to isomether having asix-membered ring orcycloparaffinic dierize the double bond in the olefinically unsaturatedether having a fiveor six-membered ring, constitute ketimines andketones produced upon hydrolysis (colpreferred embodiments of thisinvention. umns 4 and 5 of the above tabulation). Thus. if keti- Thecyclic aluminum compounds of this invention mines or ketones having adoulbe bond in a different are non-ionic. They are usually soluble inconventional position are desired, suitable isomerization proceduresaliphatic and aromatic hydrocarbon solvents such as are available foreffecting this transformation. benzene. The following examplespecifically illustrates a typi- Another feature of this invention isthe fact that the cal synthesis of a representative compound of thisinorganoaluminum compounds provided by this invenvention and its use asan intermediate in the formation tion are of particular utility asintermediates in the syn- 0f et mine and ketone products. This exampleis pres- TABLE Aluminum-Containing Cyclic I Aluminum-Containing NitrileMoiety Formed on 1:1 Addition Ketimine formed on Ketone formed on CyclicMoiety in Reactant Reactant Reaction between (1) and (2) Hydrolysis of(3) Hydrolysis of (4) aluminacyclopentd'ene butyronitrile4-vinyl-3-propyl-( l-a|umina-Z- 4-imino-5-methyl-hept-5methyl-hept-6-en-4-one azacyclopent-Z-ene) 6-ene3-methyl-aluminacyclo-pentl- 4-isopropenyl-3-( l-cyclo-hexenyl2-imino-l-(cyclo- 1-( lcyclohexenyl)-3.4 3-enecyclohexenylcarbinyl)-(l-alumina-2-hexenyl)-3,4-dimethyldimethyl-pent-4-en-2-one acetonitrileazacyclopent-Z-ene) pent-4-ene 3-ethyl-aluminaeyclo-pent-3-enecycloheptyl 4-(1-ethylvinyl)-3-cyclo-heptyl-(ll-imino-l-cyclo-heptyl-2-l-cycloheptyl2-methyI-3- cyanide alumina-Z-azacyclopent-2-ene)methyl-3-ethylbut-3-ene ethyl-but-3-en-l-une 2.3-dimethyll -alumina-1.6- 4-isopropenyl-4-methyl-3-(6- 7-iminol -cyano-8,8.9- I-cyano-8,8,9-trimethyldeceyclopent-S-ene dicyanohexcyanohexyl)-(l-alumina-Z- trimethyl-dee-Q-ene 9-en-7-one ane azacyclopent-Z-ene)3-(4methyl-pent-3-enyl)- methox- 4-[ l-(4-methyl-pent-3-enyl)-vinyll-2-imino-l-methoxy-3- l-methoxy-Il-methyl-4-(4- aluminacyclopent-Il'eneyaceto-nitrile 3-methoxycarbinyl-( l-alumina-2mcthyl-4-(4-methylpentmethylpent-3-enyl) pent-4- azacyclopent-Z-ene)3-enyl)-pent-4ene enZ-one aluminacyclopent-Bene alpha- 4-vinyl-3-(l-phenethyl)-( l-alumina- 3-imino-2-phenyl-4-2-phenyl-4-methyl-hex-5-enmethylbenzyl 2-azacyclopent-2-ene)methyl-hex-S-ene 3-one cyanide 3-methyl-aluminacyclo-penb p-4-isopropenyl-3-p-fluoro'pheny-( ll-imino-l-(pl-(p-flu0r0phenyl)-2,33-ene fluorobenzoalumina-2-aza-cyclopent-2-ene) fluorophenyl)-2r3dimethyl-but-S-en-l-one nitrile dimethylbut-3-encdillllllllllCYCiUPClill-CIIC 3.5-dime 4-vinyl-3-( 3.S-dimeth0xy-phenyl li-iminol 3.5- I-(3.S-dimethoxy-phenyl)-2-thoxyalumina-2-azacyclopent-2-enc) dimethoxyphenyH-Z-methyl-but-3-en-l-one benzonitrile methyl-butJ-ene aluminacycltpent-3-ene p-tolunitrile 4-vinyl3-p-tolyl-( l-alumina-2- l-iminol-p-tolyl-2- l-p-tolyl-2-methyl-but-Il-enazacyclopent-Z-ene)mcthyl-but-S-cne l-one 3 methyl-aluniinacyclopentstearonitrile4-isoprupenyl-3-heptadecyl-t ll8-iminol9,2(Ldimethyll9.20-dimethylhenicos-ZO-en- Il-enea|umina-Z-azacyclopent-Z-ene) henicos-EO-ene lRone ented merely for thepurposes of illustration and should not be construed in a limitingsense.

EXAMPLE Reaction of l-isobutyl-3-methyl-aluminacyclopent-3-ene withbenzonitrile followed by two-stage hydrolysis To 30 ml of a 1,4-dioxanesolution containing 25 mmoles of l-isobutyl-3-methyl-aluminacyclopent-3-ene (see U.S. Pat. No. 3,631,065) was slowly added 3.0 milliliters(approximately 29 mmoles) of freshly distilled benzonitrile. During theaddition the temperature of the stirred reaction mixture increased fromroom temperature (ca. 25C.) to 50C. and the system turned reddish brownin color. The reaction mixture was allowed to stand at room temperatureovernight. Thereupon most of the dioxane was stripped off and theresidue redissolved in diethyl ether. The organoaluminum product wasthen hydrolyzed by cooling the diethyl ether solution to about C. andadding cold water thereto followed by addition of cold dilute HCI. Theether solution was separated from the aqueous phase and found to containsome ketone product. The separated aqueous phase was extracted withfresh diethyl ether from which only a trace of ether-soluble product wasisolated. A substantial portion of the ketimine remained in solution inthe aqueous HCl and accordingly this solution was heated on a steam bathfor 30 minutes whereby, on hydrolysis of the ketimine, an oil was formedwhich was extracted from the aqueous layer by means of diethyl ether.After washing the ether extract with aqueous sodium bicarbonatesolution, the ether solution was dried over magnesium sulfate. Thereuponthe diethyl ether was stripped off and the residue was vacuum distilledwhereby 2.9 grams (16.5 mmoles) of ketone product was obtained at 100C.and 7 millimeters of mercury pressure. This amounted to a 66 percentyield of isolated product. The structure of the ketone was establishedby means of nuclear magnetic resonance and infrared spectra and theproduct was found to be l-phenyl-2.3-dimethyl-but-3-en-l -one.Accordingly, the water-soluble ketimine intermediate wasl-imino-l-phenyl-2,3-dimethylbut-3-ene.

It will be seen therefore that the cyclic organoaluminum product formedin the above addition reaction was 4-isopropenyl-l-isobutyl-3-phenyll-alumina-Z- azacyclopent-Z-ene):

isobutyl It was produced in a yield of over 66 percent. As noted above,the process of thisinvention is normally conducted in the presence of aLewis base having suitable chemical stability under the reactionconditions being utilized. in most cases the Lewis base will be employedas the principal reaction solventi.e., the reaction will be conducted inthe Lewis base selected for use. However. if desired, the reaction maybe effected in a suit- 6 lenes and the like) provided a suitable amountof the Lewis base is also present in the reaction system. Ordinarily thesystem should contain at least one or two mols of Lewis base per mol ofaluminum reactant employed. Particularly convenient Lewis bases for usein the process are tertiary amines (e.g.. trimethyl amine,

dimethylethyl amine, triethyl amine, tributyl amine, triphenyl amine.tribenzyl amine, benzyldimethyl amine. N-methyl morpholine, N,N-diethylaniline. N,N,N',N- tetramethyl methylene diamine, N.N,N',N tetramethylethylene diamine. pyridine, N-methyl pyrrolidine, triethylene diamine,quinuclidine, and the like); dialkyl ethers (e.g., dimethyl ether,diethyl ether. diisopropyl ether, methylisoamyl ether, dibutyl ether,dihexyl ether and the like); cycloparaffinic monoethers having asix-membered ring (e.g., tetrahydropyran-- -pentamethylene oxide--andring alkylated derivatives thereof); and cycloparaffinic diethers havinga fiveor six-membered ring (e.g., l, 4-dioxane. l,3-dioxolane,2-methyl2-ethyl-l .3-dioxolane; and the like); and other similarsubstances which tend not to be excessively cleaved in the reaction,such as dicyclohexyl ether, dibenzyl ether, and the like. At the lowerreaction temperatures, glycol ethers are also suitable solvents.

The relative proportions of the reactants and reaction diluents do notappear to be critical as lond as there is present a sufficient amount ofeach reactant to participate in the desired reaction.

Ordinarily the reaction will be conducted at atmospheric pressure or atthe ambient pressures encountered when conducting the reaction in aclose reaction vessel. However, when using some of the lower boilingLewis base solvents, e.g., dimethyl ether, trimethyl amine or the like,it is desirable to conduct the reaction at a high enough pressure tokeep the system in the liquid state of aggregation. Thus, pressures upto about atmospheres may be employed.

It will of course be understood that in the addition reaction thereaction mixture should be kept essentially anhydrous and that exposureof the reaction system to air should be kept at a minimum. Naturally oneshould select a reaction temperature at which the reaction proceeds at asatisfactory rate without encountering excessive adverse side reactionssuch as thermal decomposition, undesired cleavage reactions, undesiredcompetitive reactions or the like.

The period of time during which the reactants interact with each otheris susceptible to considerable variation and is generally discretionary.In general, the higher the reaction temperature, the shorter thereaction or contact time.

Exemplary of the compounds of this invention which may be produced inthe manner described above are the following:

4-vinyll -ethyl-3-octyl-( l-alumina-2-azacyclopent- 4-isopropenyll-propyl-3-benzyl-( l-alumina-Z- azacyclopeht-Z-enc) 4-isopropenyll-butyl-3,4-dimethyl-( l-alumina-Z- azacyclopent-Z-ene) 4-(l-ethylvinyl)- l -isobutyl-3-p-chlorophenyl-(lalumina-2-azacyclopent-2-ene) 4-vinyll-octadecyl-3-trichloromethyl-(l-alumina-2- azacyclopent-Z-ene) Other products of this invention andtheir synthesis and use will be clearly apparent to those skilled in theart 1 8 carbon atoms.

3. A compound according to claim 1 wherein the vinylic substituent inthe 4 position of said moiety is the isopropenyl group and thesubstituent in the 3 position of said moiety is a hydrocarbylsubstituent having up to about 18 carbon atoms.

4. A compound according to claim I wherein the vinylic substituent inthe 4 position of said moiety is the l-ethylvinyl group and thesubstituent in the 3 position of said moiety is a hydrocarbylsubstituent having up to about l8 carbon atoms.

5. A compound according to claim 1 wherein the vinylic substituent inthe 4 position of said moiety is the isopropenyl group, the 4 positionof said moiety also carries a methyl group, and the substituent in the 3position of said moiety is a hydrocarbyl substituent having up to about18 carbon atoms.

6. A compound according to claim 1 wherein the vinylic substituent inthe 4 position of said moiety is the l-(4-methylpent-3-enyl)vinyl groupand the substituent in the 3 position of said moiety is a hydrocarbylsubstituent having up to about 18 carbon atoms.

7. A compound according to claim 1 complexed with a Lewis base.

8. A compound according to claim 1 complexed with an ether or a tertiaryamine.

9. An organoaluminum compound of the formula wherein R is a hydrocarbongroup having up to about 18 carbon atoms, R, is hydrogen or an alkyl oran alkenyl group, R is hydrogen or an alkyl group, and R is acarbon-bonded group having up to about 30 carbon atoms.

10. A compound according to claim 9 wherein R is a lower alkyl group.

11. A compound according to claim 9 wherein R contains up to about 18carbon atoms.

412. A compound according to claim 9 wherein R is a lower alkyl groupand R is an alkyl, cycloalkyl, aralkyl or aryl group.

13. A compound according to claim 9 complexed with a Lewis base.

14. A compound according to claim 9 complexed with a tertiary amine, adialkyl ether, a cycloparaffinic monoether having a six-membered ring ora cycloparaftinic diether having a fiveor six-membered ring.

15. A compound according to claim 9 complexed with 1,4-dioxane.

16. A composition according to claim 9 wherein the compound is4-isopropenyl-l-isobutyl-3-phenyl-( lalumina-Z-azacyclopent-Z-ene).

17. A process of preparing an organoaluminum compound possessing a4-viny|ic-( l-alumina-Z- azacyclopent-Z-ene) moiety which comprisesreacting (i) a nonionic organoaluminum compound possessing analuminacyclopent-3-ene moiety, the moiety being attached by means of analuminum-carbon bond to a hydrocarbon group which optionally may besubstituted with no more than one additional so-bondedaluminacyclopent-3-ene moiety with (ii) a nitrile coreactive with saidmoiety so that a 1:] addition occurs therebetween, the reaction beingconducted in the presence of a stable Lewis base.

18. The process of claim 17 wherein the Lewis base is an ether or atertiary amine.

19. The process of claim 17 wherein the Lewis base is a tertiary amine,a dialkyl ether, a cycloparal'finic monoether having a six-memberedring, or a cycloparaffinic diether having a fiveor six-membered ring.

20. The process of claim 17 wherein the aluminacyclopent-3-ene moietyhas the formula H2C Cl-l r11/ wherein R is a hydrogen, alkyl or alkenylgroup, R is a hydrogen or alkyl group, and a1 is two-thirds of anequivalent of aluminium.

21. A process of preparing an organoaluminum compound possessing a4-vinylic-( l-alumina-Z- azacyclopent-Z-ene) moiety which comprisesreacting in an ether reaction medium a hydrocarbyl mononitrile and anorganoaluminum compound of the formula a fiveor six-membered ring.

1. An organoaluminum compound possessing a4-vinylic(1-alumina-2-azacyclopent-2-ene) moiety having a carbon-bondedsubstituent in the 3 position, the moiety being attached by means of analuminum-carbon bond to a hydrocarbon group having up to about 18 carbonatoms.
 2. A compound according to claim 1 wherein the vinylicsubstituent in the 4 position of said moiety is the vinyl group and thesubstituent in the 3 position of said moiety is a hydrocarbylsubstituent having up to about 18 carbon atoms.
 3. A compound accordingto claim 1 wherein the vinylic substituent in the 4 position of saidmoiety is the isopropenyl group and the substituent in the 3 position ofsaid moiety is a hydrocarbyl substituent having up to about 18 carbonatoms.
 4. A compound according to claim 1 wherein the vinylicsubstituent in the 4 position of said moiety is the 1-ethylvinyl groupand the substituent in the 3 position of said moiety is a hydrocarbylsubstituent having up to about 18 carbon atoms.
 5. A compound accordingto claim 1 wherein the vinylic substituent in the 4 position of saidmoiety is the isopropenyl group, the 4 position of said moiety alsocarries a methyl group, and the substituent in the 3 position of saidmoiety is a hydrocarbyl substituent having up to about 18 carbon atoms.6. A compound according to claim 1 wherein the vinylic substituent inthe 4 position of said moiety is the 1-(4-methylpent-3-enyl)vinyl groupand the substituent in the 3 position of said moiety is a hydrocarbylsubstituent having up to about 18 carbon atoms.
 7. A compound accordingto claim 1 complexed with a Lewis base.
 8. A compound according to claim1 complexed with an ether or a tertiary amine.
 10. A compound accordingto claim 9 wherein R is a lower alkyl group.
 11. A compound according toclaim 9 wherein R3 contains up to about 18 carbon atoms.
 12. A compoundaccording to claim 9 wherein R is a lower alkyl group and R3 is analkyl, cycloalkyl, aralkyl or aryl group.
 13. A compound according toclaim 9 complexed with a Lewis base.
 14. A compound according to claim 9complexed with a tertiary amine, a dialkyl ether, a cycloparaffinicmonoether having a six-membered ring or a cycloparaffinic diether havinga five- or six-membered ring.
 15. A compound according to claim 9complexed with 1,4-dioxane.
 16. A composition according to claim 9wherein the compound is4-isopropenyl-1-isobutyl-3-phenyl-(1-alumina-2-azacyclopent-2-ene). 17.A process of preparing an organoaluminum compound possessing a4-vinylic-(1-alumina-2-azacyclopent-2-ene) moiety which comprisesreacting (i) a nonionic organoaluminum compound possessing analuminacyclopent-3-ene moiety, the moiety being attached by means of analuminum-carbon bond to a hydrocarbon group which optionally may besubstituted with no more than one additional so-bondedaluminacYclopent-3-ene moiety with (ii) a nitrile coreactive with saidmoiety so that a 1:1 addition occurs therebetween, the reaction beingconducted in the presence of a stable Lewis base.
 18. The process ofclaim 17 wherein the Lewis base is an ether or a tertiary amine.
 19. Theprocess of claim 17 wherein the Lewis base is a tertiary amine, adialkyl ether, a cycloparaffinic monoether having a six-membered ring,or a cycloparaffinic diether having a five- or six-membered ring. 20.The process of claim 17 wherein the aluminacyclopent-3-ene moiety hasthe formula
 21. A PROCESS OF PREPARING AN ORGANOALUMINUM COMPOUNDPOSSESSING A 4-VINYLIC-(1-ALUMINA-2-ENE) MOIETY WHICH COMPRISES REACTINGIN AN ETHER REACTION MEDIUM A HYDROCARBYL MONOITRILE AND ANORGANOALUMINUM COMPOUND OF THE FORMULA
 22. The process of claim 21wherein R is a lower alkyl group.
 23. The process of claim 21 wherein Ris a lower alkyl group and the ether reaction medium is at least onedialkyl ether or cycloparaffinic monoether having a six-membered ring orcycloparaffinic diether having a five- or six-membered ring.